Multicomponent glass, glass fiber, twister and taper

ABSTRACT

Cd-free multicomponent glass to be used in particular as core glass ( 2 ) in glass fibers for optical twisters and tapers, the glass being of the lanthanide flint type and comprising the following main constituents (in mol %):  
                                           B 2 O 3     20-70         ZnO    1-15         Lanthanide oxide    1-23         ZrO 2 , and/or HfO 2      1-10         As 2 O 3     0.1-0.3

[0001] The invention relates to a multicomponent glass for light-transmitting bodies, for use as core glass in glass fibers.

[0002] Optical components using light transmission fibers as a light path are usable in variable fields. Due to the special requirements imposed on their application, only certain cadmium-containing multicomponent glasses are currently available commercially for use as core glasses in glass fibers for twisters and tapers. For example, a large difference of refractive index between core glass and cladding glass is desirable. The larger this difference, the thinner the twister or the taper can be. Furthermore, this application imposes specific requirements on, inter alia, expansion, hardness and crystallization. Glass fibers made of multicomponent glasses tending to crystallize have, for example, considerable scattering losses.

[0003] As cadmium is more and more prohibited, there is a need for cadmium-free core glasses having further comparable or better properties.

[0004] It is therefore an object of the invention to provide cadmium-free multicomponent glass composition ranges within which glass compositions can be found which are particularly suitable as core glass in twisters and tapers.

[0005] This object of the invention is realized when a multicomponent glass is characterized by the composition as defined in claim 1.

[0006] Within the indicated range of composition, particularly glasses can be produced with a refractive index n of at least 1.75 and an (American) softening point of between 525° C. and 725° C. and particularly between 600° C. and 725° C.

[0007] The invention also relates to a glass fiber for light transmission, a twister or a taper, characterized in that the core components consist of a glass having a composition as defined according to the invention. The invention also relates to night-vision binoculars with such a twister.

[0008] A characteristic feature of the composition of the (core) glass according to the invention is that it comprises B₂O₃, ZnO, La₂O₃ and/or As₂O₃, La₂O₃ or another rare earth (lanthanide) oxide, and ZrO₂ and/or HfO₂ as main constituents, and Sb₂O₃ and/or As₂O₃. La₂O₃ or another rare earth oxide (including Y₂O₃) functions as a glass shaper in this case.

[0009] The glass according to the invention preferably comprises no or a minimal quantity of oxides of Na, K, Li and Cs because they soften the glass and decrease the refractive index.

[0010] In accordance with a first embodiment, the glass complies with the composition as defined in claim 5.

[0011] In accordance with a second embodiment, the glass complies with the composition as defined in claim 6.

[0012] In accordance with a third embodiment, the glass complies with the composition as defined in claim 7.

[0013] A characteristic feature of the first embodiment is the slightly higher refractive index n which may range between 1.75 and 1.79, in combination with favorable values of the coefficient of expansion α (30° C. to 300° C.) which may be in the range of 67 to 73×10⁻⁷ K⁻¹, and the viscosity (American softening point ranging between 675° C. and 725° C.).

[0014] A characteristic feature of the second embodiment is the even slightly higher refractive index (1.76 to 1.79) in combination with a value of α in the range of 63 to 71×10⁻⁷ K⁻¹, and an American softening point of between 600° C. and 690° C.

[0015] A characteristic feature of the third embodiment are the even higher values of the refractive index that can be achieved, in combination with a value of α in the range of 65 to 73×10⁻⁷ K⁻¹, and an American softening point of between 650° C. and 725° C.

[0016] The main constituents in said compositions are necessary to give the Cd-free core glass its basic properties.

[0017] The optional constituents defined in the claims are used to fine-tune the basic properties and/or to give the glass extra properties without its properties being affected.

[0018] For the envisaged object, a glass having the composition as defined in claim 8 has been found to be very suitable, which a refractive index n of 1.8, an American softening point at 718° C. and an intrinsic transmission Ti of at least 0.99. Core glass rods may be drawn from molten liquid having the desired composition. An alternative is to mold the molten liquid in special molds. Light transmission glass fibers can be manufactured by means of the core glass according to the invention and a cladding glass in accordance with known methods, for example, a double crucible method or a rod-in-tube method. A bundle of fibers can be made from a plurality of glass fibers. By twisting a bundle of fibers, a twister is obtained. This twister rotates the image coming from, for example, a photomultiplier and is used in night-vision telescopes. To be able to comply with all of these manufacturing steps, a special core glass is necessary which must also be free from Cd in the present case. A bundle of fibers, which is twisted or not twisted, can also be given a cross-section extending from small to large. Then a bundle of fibers referred to as taper is concerned.

[0019] These and other aspects of the invention are apparent from and will be elucidated with reference to the embodiments described hereinafter.

[0020] In the drawings:

[0021]FIG. 1 shows diagrammatically the arrangement of a twister in night-vision telescope;

[0022]FIG. 2 shows diagrammatically a twister;

[0023]FIG. 3 is a diagrammatic plan view of a twister;

[0024]FIG. 4 is an enlarged detail of FIG. 3, and

[0025]FIG. 5 is an enlarged detail of FIG. 4.

[0026] A general embodiment of a night-vision telescope 10 (FIG. 1) is provided with a power supply 11, a fiber-optical system 12 with an entrance face 13 on which photons are incident, and an exit face provided with a photocathode 14. Electrons e emitted by the photocathode 14 are multiplied in the MCP device. The multiplied electrons are incident on a phosphor layer 15. The phosphor layer 15 emits photons which go from an entrance face 17 of the twister via bundled transmission fibers to an exit face 18.

[0027] The transmission fibers of the twister 16 shown in greater detail in FIGS. 2 and 3 not only comprise core glass 2 according to the invention but also cladding glass 3, EMA (a strongly absorbing glass) 4 and, in some cases, an envelope glass enclosing the cylindrical twister 16 like a cladding (FIG. 5). In practice, the cladding glass 3 often has a refractive index of approximately 1.5. A suitable material is, for example, Schott 8250. The core glass 2 according to the invention will be described hereinafter. Based on the inventors' recognition, this core glass must preferably comply with one or more of the following requirements, when used in twisters:

[0028] 1. refractive index n at least 1.75 (at a light wavelength of 598.29 nm)

[0029] 2. coefficient of expansion (30° C. to 300° C.) 60 to 80×10⁻⁷ K⁻¹

[0030] 3. no crystallization during molding

[0031] 4. Ti at least 0.95 at 25 mm (Ti is the intrinsic transmission, i.e. without surface losses)

[0032] 5. viscosity: (American) softening point between 600° C. and 725° C.

[0033] Example:

[0034] A plurality of core glasses of different compositions within the ranges of composition according to the invention were made in the shape of rods. The compositions and the physical values measured on the rods are given below. Sample 0 Sample 00 calc. calc. meas. calc. calc. meas. mol % wt % wt % mol % wt % wt % Chemical Composition SiO₂ 3.0 3.0 1.3 1.5 B₂O₃ 60.5 60.5 30.9 30.9 Al₂O₃ 1.5 1.5 1.1 1.2 ZnO 3.5 3.5 2.1 2.3 CdO 10.0 PbO 10.0 16.4 17.2 La₂O₃ 17.0 17.0 40.6 39.0 TiO₂ 0.0 ZrO₂ 3.0 3.0 2.7 2.6 Ta₂O₅ 1.5 1.5 4.9 5.3 Refr.index 1.755 1.773 n Absorption [cm⁻¹] 480 nm 0.008 0.008 540 nm 0.004 0.004 620 nm 0.004 — 700 nm 0.004 — Fiber viscosity [° C.] Strain point 634 605 Annealing 640 610 point Philips 646 615 softening Point American 703 670 Softening point Expansion 66 67 30-300 [° C.*10⁻⁷] Sample 1 Sample 2 Chemical composition (mol %) SiO₂ — 10.5 B₂O₃ 55.0 45.1 BaO 0.3 0.2 ZnO 13.2 13.0 PbO 4.5 4.1 Y₂O₃ 5.7 5.6 La₂O₃ 12.3 12.1 Sb₂O₃ 0.04 0.13 ZrO₂ 6.6 6.5 Nb₂O₅ 2.8 2.8 SO₃ 0.05 Refr.index 1.800 1.800 n Ti 25 mm thickness 480 nm 0.99 540 nm 1.00 620 nm 1.00 700 nm 1.00 Fiber viscosity [° C.] Strain point 622 612 Annealing point 630 627 Philips softening point 634 633 American softening point 688 718 Sample Sample Sample Sample Sample 3 4 5 6 7 Chemical composition (mol %) SiO₂ — 5.0 0.0 5.0 10.5 B₂O₃ 49.8 44.8 44.8 49.8 45.1 Al₂O₃ 5.0 5.0 10.0 0.1 BaO 0.2 0.2 0.3 0.2 3.5 ZnO 13.1 13.1 13.1 13.1 13.0 PbO 4.4 4.5 4.4 4.5 4.1 Y₂O₃ 5.6 5.6 5.6 5.6 5.6 La₂O₃ 12.3 12.3 12.3 12.3 12.1 Sb₂O₃ 0.04 0.04 0.04 0.04 0.13 ZrO₂ 6.6 6.6 6.6 6.6 3.3 Nb₂O₅ 2.8 2.8 2.8 2.8 2.8 Fiber viscosity [° C.] Strain point 604 622 Annealing point 616 630 Philips softening point 622 634 American softening point 700 694 Sample 30 Sample 31 calc. calc. meas. calc. calc. meas. mol % wt % wt % mol % wt % wt % Chemical composition SiO₂ 33.2 16.5 8.2 3.7 B₂O₃ 24.3 14.0 56.1 29.4 Al₂O₃ 6.3 5.3 1.2 Na₂O K₂O CaO BaO 0.3 0.3 0.3 0.3 ZnO 2.5 1.7 2.1 1.3 CdO PbO 30.6 56.3 2.8 4.7 Fe₂O₃ Y₂O₃ 3.7 6.2 La₂O₃ 1.6 4.3 19.2 47.2 Sb₂O₃ 0.04 0.1 0.1 0.1 TiO₂ ZrO₂ 1.6 1.6 7.7 7.1 V₂O₅ Nb₂O₅ Ta₂O₅ WO₃ F— 1.9 0.3 Refr.index 1.749 1.755 n Absorption [cm⁻¹] 480 nm 0.027 0.008 540 nm 0.008 0.003 620 nm 0.017 0.002 700 nm 0.007 0.001 Fiber viscosity [° C.] Strain point Annealing point Philips softening point American softening point Sample 32 Sample 33 calc. calc. meas. calc. calc. meas. mol % wt % wt % mol % wt % wt % Chemical composition SiO₂ 3.3 1.5 B₂O₃ 61.0 31.3 49.6 27.0 Al₂O₃ Na₂O K₂O CaO 4.4 1.9 BaO 0.3 0.3 6.5 7.8 ZnO 4.3 2.6 5.6 3.6 CdO PbO 1.9 3.4 Fe₂O₃ Y₂O₃ 5.3 8.8 1.6 2.8 La₂O₃ 18.9 45.5 14.2 36.3 Sb₂O₃ 0.1 0.1 0.04 0.1 TiO₂ 2.6 1.6 ZrO₂ 7.9 7.2 6.8 6.5 V₂O₅ Nb₂O₅ 1.7 3.3 3.6 7.6 Ta₂O₅ WO₃ 0.7 1.2 F— 10.7 1.5 Refr.index 1.789 1.807 n Absorption [cm⁻¹] 480 nm 0.035 0.017 540 nm 0.016 0.005 620 nm 0.030 0.003 700 nm 0.014 0.001 Fiber viscosity [° C.] Strain point Annealing point Philips softening point American softening point Sample 34 Sample 35 calc. calc. meas. calc. calc. Meas. mol % wt % wt % mol % wt % Wt % Chemical composition SiO₂ 8.0 4.2 B₂O₃ 55.0 30.0 55.5 33.6 Al₂O₃ Na₂O K₂O CaO BaO 0.3 0.3 0.3 0.3 ZnO 13.2 8.4 11.3 8.0 CdO PbO 4.5 7.8 Fe₂O₃ Y₂O₃ 5.7 10.0 2.3 4.5 La₂O₃ 12.3 31.4 12.6 35.7 Sb₂O₃ 0.04 0.1 0.04 0.1 TiO₂ ZrO₂ 6.6 6.4 7.8 8.4 V₂O₅ Nb₂O₅ 2.8 5.9 2.4 5.5 Ta₂O₅ WO₃ F— Refr.index 1.800 1.760 n Absorption [cm⁻¹] 480 nm 0.011 540 nm 0.004 620 nm 0.002 700 nm 0.001 Fiber viscosity [° C.] Strain point 622 Annealing 630 point Philips 634 softening point American 688 softening point

[0035] In summary, the invention relates to a Cd-free multicomponent glass, particularly for use as a core glass in transmission fibers for optical twisters, tapers, etc., which glass is of the lanthanide flint type and comprises the following main constituents (in mol %): B₂O₃ 20-70 ZnO  1-15 Lanthanide oxide  1-23 ZrO₂, and/or HfO₂  1-10 As₂O₃ 0.1-0.3 

1. A multicomponent glass for light-transmitting bodies for use as a core glass in glass fibers, characterized in that the glass is a glass of the lanthanide flint type having the following composition in mol %: SiO₂  0-40 B₂O₃ 20-70 ZnO  1-15 PbO  0-35 Lanthanide oxide  1-23 ZrO₂ and/or HfO₂  1-10 MgO and/or CaO 0-7 SrO and/or BaO 0-9 TiO₂ 0-4 Sb₂O₃ and/or As₂O₃ 0.1-0.3 Nb₂O₅ 0-5 Ta₂O₅ 0-3 WO₃ 0-2 Al₂O₃ 0-8 F  0-15

without CdO, with a refractive index n=at least 1.74, an American softening point of between 525° C. and 725° C., and a coefficient of expansion of between 30° C. and 300° C. of between 60 and 80×10⁻⁷.
 2. A glass fiber for light transmission, characterized in that the core component comprises a glass as claimed in claim
 1. 3. A twister for light transmission, characterized in that the core component comprises a glass as claimed in claim
 1. 4. A taper for light transmission, characterized in that the core component comprises a glass as claimed in claim
 1. 5. A multicomponent glass as claimed in claim 1, having the following composition SiO₂  5-10 B₂O₃ 50-60 Al₂O₃ 0-1 ZnO 1-5 PbO 0-5 Y₂O₃ 2-5 La₂O₃ 16-23 ZrO₂ 6-9 CaO 0-1 BaO 0-1 CaO + BaO 0-1 TiO₂ 0-1 Nb₂O₅ 0-2 Ta₂O₅ 0-2 WO₃ 0-2 Nb₂O₅ + Ta₂O₅ + WO₃ 0-2 Sb₂O₃ 0.1-0.3 F 0-2


6. A multicomponent glass as claimed in claim 1, having the following composition SiO₂ 0-5 B₂O₃ 54-65 Al₂O₃ 0-3 ZnO 2-6 PbO  8-12 Y₂O₃ 0-1 La₂O₃ 14-20 ZrO₃ 1-5 CaO 0-1 BaO 0-3 CaO + BaO 0-3 TiO₂ 0-1 Nb₂O₅ 0-2 Ta₂O₅ 0-4 WO₃ 0-2 Nb₂O₅ + Ta₂O₅ + WO₃ 0-4 Sb₂O₃ 0.1-0.3 F 0-2


7. A multicomponent glass as claimed in claim 1, having the following composition SiO₂  0-12 B₂O₃ 45-60 Al₂O₃ 0-1 ZnO 10-15 PbO 3-6 Y₂O₃ 4-7 La₂O₃ 10-15 ZrO₂ 5-7 CaO 0-1 BaO 0-1 CaO + BaO 0-1 TiO₂ 0-1 Nb₂O₅ 2-4 Ta₂O₅ 0-2 WO₃ 0-2 Nb₂O₅ + Ta₂O₅ + WO₃ 2-4 Sb₂O₃ 0.1-0.3 F 0-2


8. A multicomponent glass as claimed in claim 7, having the following composition Chemical SiO₂ 10.5 composition B₂O₃ 45.1 (mol %) Al₂O₃ BaO 0.2 ZnO 13.0 PbO 4.1 Y₂O₃ 5.6 La₂O₃ 12.1 Sb₂O₃ 0.13 CeO₂ ZrO₂ 6.5 HfO₂ Nb₂O₅ 2.8 Ta₂O₅


9. Night-vision telescope provided with a twister as claimed in claim
 3. 